Process for applying protectiive and decorative coating on an article

ABSTRACT

A method for depositing a multi-layered protective and decorative coating on an article comprising first depositing at least one coating layer on the article by electroplating, removing the electroplated article from the electroplating bath and subjecting it to pulse blow drying to produce a spot-free surface on the electroplated article, and then depositing, by physical vapor deposition, at least one vapor deposited coating layer on the electroplated article.  
     The electroplated layers are selected from copper, nickel and chrome. The physical vapor deposited layers are selected from non-precious refractory metals, non-precious refractory metal alloys, non-precious refractory metal compounds, and non-precious refractory metal alloy compounds.

FIELD OF THE INVENTION

[0001] The present invention is directed to a method of applyingprotective and decorative coatings to articles

BACKGROUND OF THE INVENTION

[0002] Providing an article such as, for example, a brass faucet or lockwith a multilayered coating by depositing a first coating layer orseries of coating layers by electroplating and then depositing a secondcoating layer or series of coating layers on the electroplated coatinglayer by physical vapor deposition is known in the art. Such amultilayered coating provides abrasion and corrosion protection to thearticle, is decorative, and levels off any imperfections such as nicksand scratches on the article. Thus, for example, a brass article havinga duplex nickel layer comprised of bright nickel and semi-bright nickelelectroplated thereon and a zirconium nitride layer deposited on theduplex nickel layer by physical vapor deposition is smooth, has improvedabrasion and corrosion resistance, and has the color of polished brass.

[0003] It is generally the vapor deposited layer which provides theabrasion protection and decorative appearance. However, the vapordeposited coating layer is generally quite thin, typically in the rangeof from about one to 20 millionths of an inch. Due to the thinness ofthe vapor deposited coating any water spots or any other surface defectssuch as nickel or chrome stains from or caused by the electroplatingprocess show through and indeed are accentuated by the thin vapordeposited coating. Even spots, stains or discolorations which are notvisible to the naked eye on the electroplated article will becomevisible after the vapor deposited coating is applied.

[0004] It is thus currently necessary to thoroughly inspect, clean anddry each article as it comes out of the electroplating bath. Oneconventional way of cleaning the electroplated articles is to run thearticles through a water based cleaning system and use nitrogen dryingto dry the articles. This is quite expensive and not always successful.Another method involves hand drying and cleaning each individualarticle. This hand drying, while more effective than a nitrogen baseddrying system, is very labor intensive and, therefore, also quiteexpensive. Hand drying also involves handling the electroplated articleswhich may result in dropping or bumping the articles against otherobjects with consequent damage to the articles.

[0005] It would be very advantageous if an efficient and effectivedrying method for the electroplated articles were available whicheliminated the problems associated with conventional, currently usedcleaning and drying methods. It is an object of the instant invention toprovide such a system.

SUMMARY OF THE INVENTION

[0006] The instant invention comprises a method of applying a multilayer protective and decorative coating to an article. The methodinvolves first applying at least one coating layer by electroplating.The electroplated article is then removed from the electroplating bathand subjected to pulse blow drying for spot-free drying. The driedelectroplated article is then placed in a vapor deposition chamber andat least one coating layer is vapor deposited on the electroplatedarticle.

[0007] The electroplating comprises applying at least one layer selectedfrom copper, nickel and chrome. The copper plating includes bothalkaline copper plating and acid copper plating. The nickel platingincludes the electroplating of bright nickel, semi-bright nickel, and aduplex nickel layer comprised of bright nickel and semi-bright nickel.

[0008] Before the electroplated article is subjected to a vapordeposition process in order to apply at least one thin vapor depositedcoating layer onto the electroplated coating the article is pulse blowdried in order to remove any wet spots or nickel or chrome stains.

[0009] After pulse blow drying at least one coating layer is depositedby physical vapor deposition onto the top electroplated layer. The vapordeposited layer or layers are selected from non-precious refractorymetals, non-precious refractory metal alloys, non-precious refractorymetal compounds, and non-precious refractory metal alloy compounds. Thenon-precious refractory metal compounds and non-precious refractorymetal alloy compounds include the nitrides, oxides, carbides,carbonitrides, and reaction products of a refractory metal or refractorymetal alloy, oxygen and nitrogen.

BRIEF DESCRIPTION OF THE DRAWINGS

[0010]FIG. 1 is a cut away perspective view of a pulse blow dryer;

[0011]FIG. 2 is a cross-sectional view, not to scale, of a portion ofthe substrate having the electroplated coating layers thereon;

[0012]FIG. 3 is a view similar to FIG. 2 but showing another embodimentof the invention with a different arrangement of the electroplatedcoating layers;

[0013]FIG. 4 is a cross-sectional view, not to scale, showing onearrangement of the physical vapor deposited layers;

[0014]FIG. 5 is a view similar to FIG. 4 but showing another embodimentof the invention with a different arrangement of different physicalvapor deposited layers; and

[0015]FIG. 6 is a cross-sectional view, not to scale, of a portion ofthe substrate having the electroplated and physical vapor depositedcoating layers thereon.

DESCRIPTION OF THE PREFERRED EMBODIMENT

[0016] The method of this invention is especially characterized byproviding a decorative and protective vapor deposited thin coating layeron an electroplated undercoating which is free of blemishes orimperfections such as water spots, nickel spots and chrome spots. Theseblemishes or imperfections are generally due to spots remaining on theelectroplated surface of the article as a result of the electroplatingprocess. When the thin vapor deposited coating layer is applied overthese spots they are greatly accentuated by this thin physical vapordeposited coating layer.

[0017] The method of the instant invention comprises first depositing onat least a portion of the surface of an article at least oneelectroplated coating layer, removing the electroplated article from theelectroplating bath and subjecting it to pulse blow drying to remove anyspots from the surface thereof, and applying, by physical vapordeposition, at least one thin coating layer onto the clean and dryelectroplated surface.

[0018] Pulse blow drying and a pulse blow dryer are described inEuropean Patent 0 486 711, the disclosure of which is incorporatedherein by reference. The pulse blow dryer is illustrated in FIG. 1.Briefly it comprises a housing similar to a conventional and well knowncirculating air drier. Ventilator, heating device, and air circulationshutters correspond to known and conventional designs. A movable nozzledevice is additionally installed at each side of the station. The nozzledevice is equipped with little nozzle pipes, about 150 mm long, andprovided with 15 borings which correspond to the width of the traveldirection. Each little nozzle pipe is supplied with air by means ofsolenoid valves. The solenoid valves are controlled by a microprocessorallowing the valves to be opened one after the other. The openingintervals can be adjusted between 20 and 100 ms via the control device.In case of wide driers, the valves are opened in groups, i.e. from 6-8little nozzle pipes, one pipe is always open. The nozzle devices aremoved up and down in opposite direction with an adjustable speed. Thespeed is normally approximately one to two strokes per minute. Thestroke corresponds to the height of the rack plus 50 mm on top andbottom.

[0019] By the pulse-like connection of the individual little nozzlepipes to the compressed air supply with a nominal pressure of six bars,15 air jets/pipe will result. These air jets atomize the water dropletson the surface of the parts. Due to the repeated blowing off of thesurface of the articles with the pulsating air jets and stepping on fromnozzle pipe to nozzle pipe in the horizontal position, one air jet isgenerated for approximately 1 cm² of surface.

[0020] The alternating passing and blowing-in of the sharp air jets intoborings, blindholes, undercuts, and edges lead to a suction effect whichremoves the liquid even from the hollow spaces. This effect is sointense that even long borings in hollow parts, large interior spacesand threaded holes are dried well. When removing the parts from theracks, no water flows out from the hollow spaces and thus the quality ofthe surface is not spoiled by water stains.

[0021] A programmable control device allows a selection of the pulsefrequency, the speed of the nozzle device, the number of valvessimultaneously opened, the number of strokes, and the temperature. Theseparameters can be assigned to the articles to be treated. In a dryingprogram, the speed and pulse frequency can be separately adjusted forevery stroke. Large articles with a great drag-out can be blown off veryquickly at the first stroke with short air pulses. The main quantity ofadhesive water droplets is blown off here.

[0022] During the following strokes, the speed will be automaticallyreduced and the pulse frequency will be extended. The stronger airpulses and the valves opened for a longer period have a considerablybetter suction effect resulting in an improved drying of the hollowspaces.

[0023] As the main quantity of water is blown off, i.e. atomized, only avery thin adsorption layer remains to be dried up. Therefore, only shortdrying periods of two to five minutes are needed at a circulating airtemperature of 50-70° C.

[0024] The pulse blow drying provides stainless drying. Thuselectroplated articles can have a physical vapor deposited thin coatingapplied thereon without any further cleaning or drying of theelectroplated articles.

[0025] The article can be comprised of any platable substrate such asmetal or plastic. The metals that the article can be comprised ofinclude brass, zinc, steel and aluminum. The electroplated coating whichis deposited by electroplating on at least a portion of the surface ofthe article can be comprised of one layer or more than one layer.Preferred electroplated coatings include copper, including alkalinecopper and acid copper, nickel, including bright nickel and semi-brightnickel, and chrome.

[0026] If the article is comprised of brass typically at least onenickel layer and chrome layer are electroplated on said article, withthe nickel layer being deposited directly on the surface of the articleand the chrome layer being deposited on the nickel layer. Brass articlescan also have a copper layer applied directly on the surface thereof. Atleast one nickel layer is then electroplated on the copper layer. Achrome layer is then electroplated on the nickel layer.

[0027] The nickel layer is deposited on at least a portion of thesurface of the substrate article by conventional and well knownelectroplating processes. These processes include using a conventionalelectroplating bath such as, for example, a Watts bath as the platingsolution. Typically such baths contain nickel sulfate, nickel chloride,and boric acid dissolved in water. All chloride, sulfamate andfluoroborate plating solutions can also be used. These baths canoptionally include a number of well known and conventionally usedcompounds such as leveling agents, brighteners, and the like. To producespecularly bright nickel layer at least one brightener from class I andat least one brightener from class II is added to the plating solution.Class I brighteners are organic compounds which contain sulfur. Class IIbrighteners are organic compounds which do not contain sulfur. Class IIbrighteners can also cause leveling and, when added to the plating bathwithout the sulfur-containing class I brighteners, result in semi-brightnickel deposits. These class I brighteners include alkyl naphthalene andbenzene sulfonic acids, the benzene and naphthalene di- and trisulfonicacids, benzene and naphthalene sulfonamides, and sulfonamides such assaccharin, vinyl and allyl sulfonamides and sulfonic acids. The class IIbrighteners generally are unsaturated organic materials such as, forexample, acetylenic or ethylenic alcohols, ethoxylated and propoxylatedacetylenic alcohols, coumarins, and aldehydes. These class I and classII brighteners are well known to those skilled in the art and arereadily commercially available. They are described, inter alia, in U.S.Pat. No. 4,421,611 incorporated herein by reference.

[0028] The nickel layer can be a monolithic layer comprised of, forexample, semi-bright nickel or bright nickel; or it can be a duplexlayer containing a layer comprised of semi-bright nickel and a layercomprised of bright nickel. The thickness of the nickel layer isgenerally in the range of from about 100 millionths (0.000100) of aninch, preferably about 150 millionths (0.000150) of an inch to about3,500 millionths (0.0035) of an inch.

[0029] As is well known in the art before the nickel layer is depositedon the substrate the substrate is subjected to said activation by beingplaced in a conventional and well known acid bath.

[0030] In one embodiment as illustrated in FIG. 2, the nickel layer 13is actually comprised of two different nickel layers 14 and 16. Layer 14is comprised of semi-bright nickel while layer 16 is comprised of brightnickel. This duplex nickel deposit provides improved corrosionprotection to the underlying substrate. The semi-bright, sulfur-freeplate 14 is deposited, by conventional electroplating processes,directly on the surface of the article substrate 12. The substrate 12containing the semi-bright nickel layer 14 is then placed in a brightnickel plating bath and the bright nickel layer 16 is deposited on thesemi-bright nickel layer 14.

[0031] The thickness of the semi-bright nickel layer and the brightnickel layer is a thickness effective to provide improved corrosionprotection. Generally, the thickness of the semi-bright nickel layer isat least about 50 millionths (0.00005) of an inch, preferably at leastabout 100 millionths (0.0001) of an inch, and more preferably at leastabout 150 millionths (0.00015) of an inch. The upper thickness limit isgenerally not critical and is governed by secondary considerations suchas cost. Generally, however, a thickness of about 1,500 millionths(0.0015) of an inch, preferably about 1,000 millionths (0.001) of aninch, and more preferably about 750 millionths (0.00075) of an inchshould not be exceeded. The bright nickel layer 16 generally has athickness of at least about 50 millionths (0.00005) of an inch,preferably at least about 125 millionths (0.000125) of an inch, and morepreferably at least about 250 millionths (0.00025) of an inch. The upperthickness range of the bright nickel layer is not critical and isgenerally controlled by considerations such as cost. Generally, however,a thickness of about 2,500 millionths (0.0025) of an inch, preferablyabout 2,000 millionths (0.002) of an inch, and more preferably about1,500 millionths (0.0015) of an inch should not be exceeded. The brightnickel layer 16 also functions as a leveling layer which tends to coveror fill in imperfections in the substrate.

[0032] In another embodiment of the invention as illustrated in FIG. 2 achrome layer 20 is electroplated onto the nickel layer 13. The chromelayer 20 may be deposited on the nickel layer 13 by conventional andwell known chromium electroplating techniques. These techniques, alongwith various chrome plating baths, are disclosed in Brassard,“Decorative Electroplating—A Process in Transition”, Metal Finishing,pp. 105-108, June 1988; Zaki, “Chromium Plating”, PF Directory, pp.146-160; and in U.S. Pat. Nos. 4,460,438, 4,234,396, and 4,093,522, allof which are incorporated herein by reference.

[0033] Chrome plating baths are well known and commercially available. Atypical chrome plating bath contains chromic acid or salts thereof, andcatalyst ion such as sulfate or fluoride. The catalyst ions can beprovided by sulfuric acid or its salts and fluosilicic acid. The bathsmay be operated at a temperature of about 112°-116° F. Typically inchrome plating a current density of about 150 amps per square foot, atabout 5 to 9 volts is utilized.

[0034] The chrome layer generally has a thickness of at least about 2millionths (0.000002) of an inch, preferably at least about 5 millionths(0.000005) of an inch, and more preferably at least about 8 millionths(0.000008) of an inch. Generally, the upper range of thickness is notcritical and is determined by secondary considerations such as cost.However, the thickness of the chrome layer should generally not exceedabout 60 millionths (0.00006) of an inch, preferably about 50 millionths(0.00005) of an inch, and more preferably about 40 millionths (0.00004)of an inch.

[0035] In another embodiment of the invention, as illustrated in FIG. 3,especially when the substrate article is comprised of zinc or brass, acopper layer 17 or layers are electroplated on at least a portion of thearticle surface 12. Nickel layer 16 is then electroplated on the copperfollowed by electroplating of chrome 20 on the nickel layer. The nickellayer may be a monolithic layer as illustrated in FIG. 3 and comprisedof, for example, bright nickel or it may be a duplex nickel layercomprised of, for example, a bright nickel layer and a semi-brightnickel layer. The copper coating 17 may be comprised of a monolithiccopper layer or two different copper layers, for example, an alkalinecopper layer on the surface of the article and an acid copper layer onthe alkaline copper layer. In the embodiment illustrated in FIG. 3 thecopper coating 17 is a monolithic copper layer comprised of acid copper.

[0036] Copper electroplating processes and copper electroplating bathsare conventional and well known in the art. They include theelectroplating of acid copper and alkaline copper. They are described,inter alia, in U.S. Pat. Nos. 3,725,220; 3,769,179; 3,923,613; 4,242,181and 4,877,450, the disclosures of which are incorporated herein byreference.

[0037] The preferred copper layer is selected from alkaline copper andacid copper. The copper layer may be monolithic and consist of one typeof copper such as alkaline copper or acid copper, or it may comprise twodifferent copper layers such as a layer comprised of alkaline copper 11a and a layer comprised of acid copper 11 b.

[0038] The thickness of the copper layer is generally in the range offrom at least about 100 millionths (0.0001) of an inch, preferably atleast about 150 millionths (0.00015) of an inch to about 3,500millionths (0.0035), preferably about 2,000 millionths (0.002) of aninch.

[0039] When a duplex copper layer is present comprised of, for example,an alkaline copper layer and an acid copper layer, the thickness of thealkaline copper layer is generally at least about 50 millionths(0.00005) of an inch, preferably at least about 75 millionths (0.000075)of an inch. The upper thickness limit is generally not critical.Generally, a thickness of about 1,500 millionths (0.0015) of an inch,preferably about 1,000 millionths (0.001) of an inch should not beexceeded. The thickness of the acid copper layer is generally at leastabout 50 millionths (0.0005) of an inch, preferably at least about 75millionths (0.00075) of an inch. The upper thickness limit is generallynot critical. Generally, a thickness of about 1,500 millionths (0.0015)of an inch, preferably about 1,000 millionths (0.001) of an inch shouldnot be exceeded.

[0040] Some illustrative, non-limiting examples of electroplated layersinclude substrate/nickel such as bright nickel/chrome,substrate/semi-bright nickel/bright nickel/chrome, substrate/nickel suchas bright nickel, substrate/semi-bright nickel/bright nickel,substrate/copper such as acid copper/nickel such as brightnickel/chrome, substrate/alkaline copper/acid copper/nickel such asbright nickel/chrome, substrate/copper such as alkalinecopper/semi-bright nickel/bright nickel/chrome, substrate/alkalinecopper/acid copper/semi-bright nickel/bright nickel/chrome,substrate/copper such as acid copper/nickel such as bright nickel,substrate/copper such as alkaline copper/semi-bright nickel/brightnickel, and substrate/alkaline copper/acid copper/semi-brightnickel/bright nickel.

[0041] After the article has had the various electroplated coatinglayers, as exemplified supra and in FIGS. 2 and 3, deposited thereon byelectroplating it is then subjected to pulse blow drying to blow off anyspots, stains, moisture or droplets and produce an electroplated articlehaving a stainless top surface. After completion of the pulse blowdrying the electroplated article is placed in a physical vapordeposition chamber and one or more thin coating layers are deposited byphysical vapor deposition on the surface of the electroplated article.

[0042] The layers which are deposited by physical vapor deposition aremetallic layers and are selected from non-precious refractory metals,non-precious refractory metal alloys, non-precious refractory metalcompounds, and non-precious refractory metal alloy compounds. Thenon-precious refractory metals include hafnium, tantalum, titanium andzirconium. The preferred refractory metals are titanium and zirconium,with zirconium being more preferred. The non-precious refractory metalalloys include the alloys of the above mentioned refractory metals withthe binary alloys being preferred. The preferred binary alloys are thebinary alloys of zirconium, with the binary alloys of zirconium andtitanium being more preferred.

[0043] The non-precious refractory metal and metal alloy compoundsinclude the nitrides, oxides, carbides and carbonitrides of thenon-precious refractory metals and metal alloys. Also included among thenon-precious refractory metal and metal alloy compounds useful in theinstant invention are the reaction products of a non-precious refractorymetal or metal alloy, oxygen and nitrogen. Examples of thesenon-precious refractory metal compounds include zirconium nitride,zirconium oxide, zirconium carbide, zirconium carbonitride, reactionproducts of zirconium, oxygen and nitrogen, titanium nitride, titaniumoxide, titanium carbonitride, reaction products of titanium, oxygen andnitrogen, hafnium nitride, hafnium oxide, hafnium carbonitride, tantalumoxide, tantalum nitride, tantalum carbide, and the like.

[0044] The reaction products of a non-precious refractory metal, such asfor example zirconium, oxygen and nitrogen comprise zirconium oxide,zirconium nitride and zirconium oxy-nitride.

[0045] Some illustrative non-limiting examples of the non-preciousrefractory metal alloy compounds include zirconium-titanium nitride,zirconium-titanium oxide, zirconium-titanium carbide, zirconium-titaniumcarbonitride, hafnium-zirconium nitride, hafnium-tantalum oxide,tantalum-titanium carbide, and reaction products of zirconium-titaniumalloy, oxygen and nitrogen.

[0046] The layers comprised of refractory metals and refractory metalalloys are deposited on at least a portion of the surface of theelectroplated article by conventional and well known physical vapordeposition processes such as, for example, ion sputtering, cathodic arcelectron evaporation beam deposition, and the like. Ion sputteringtechniques and equipment are disclosed, inter alia, in T. Van Vorous,“Planar Magnetron Sputtering; A New Industrial Coating Technique”, SolidState Technology, December 1976, pp. 62-66; U. Kapacz and S. Schulz,“Industrial Application of Decorative Coatings—Principle and Advantagesof the Sputter Ion Plating Process”, Soc. Vac. Coat., Proc. 34th Arn.Tech. Conf., Philadelphia, U.S.A., 1991, 48-61; J. Vossen and W. Kern“Thin Film Processes II”, Academic Press, 1991; R. Boxman et al,“Handbook of Vacuum Arc Science and Technology”, Noyes Pub., 1995; andU.S. Pat. Nos. 4,162,954 and 4,591,418, all of which are incorporatedherein by reference.

[0047] Briefly, in the sputtering deposition process the refractorymetal such as titanium or zirconium target, which is the cathode, andthe substrate are placed in a vacuum chamber. The air in the chamber isevacuated to produce vacuum conditions in the chamber. An inert gas,such as Argon, is introduced into the chamber. The gas particles areionized and are accelerated to the target to dislodge titanium orzirconium atoms. The dislodged target material is then typicallydeposited as a coating film on the substrate.

[0048] In cathodic arc evaporation an electric arc of typically severalhundred amperes is struck on the surface of a metal cathode such aszirconium or titanium. The arc vaporizes the cathode material, whichthen condenses on the substrate forming a coating.

[0049] Reactive ion sputtering is generally similar to ion sputterdeposition except that a reactive gas such as, for example, oxygen ornitrogen which reacts with the dislodged target material is introducedinto the chamber. Thus, in the case where zirconium nitride is a layerthe target is comprised of zirconium and nitrogen gas is the reactivegas introduced into the chamber. By controlling the amount of nitrogenavailable to react with the zirconium, the color of the zirconiumnitride can be made to be similar to that of brass of various hues.

[0050] Generally, more than one layer comprised of refractory metal,refractory metal alloy, refractory metal compound and refractory metalalloy compound is deposited on the electroplated article. Thus, forexample, a layer comprised of refractory metal or refractory metal alloysuch as zirconium is vapor deposited on the electroplated article; asandwich layer comprised of alternating layers of refractory metal orrefractory metal alloy such as zirconium and refractory metal compoundor refractory metal alloy compound such as zirconium nitride is thendeposited on the zirconium layer; and a layer comprised of the reactionproducts of a refractory metal or refractory metal alloy such aszirconium, oxygen and nitrogen is deposited on the sandwich layer.

[0051] In another embodiment a layer comprised of a first refractorymetal compound or refractory metal alloy compound, preferably a nitride,is vapor deposited on the refractory metal or refractory metal alloylayer. A layer comprised of a different second refractory metal compoundor refractory metal alloy compound, preferably an oxide or the reactionproducts of a refractory metal or refractory metal alloy, oxygen andnitrogen, is then vapor deposited on said first refractory metalcompound or refractory metal alloy compound layer.

[0052] Generally the refractory metal or refractory metal alloy layerhas a thickness of at least about 0.25 millionths (0.00000025) of aninch, preferably at least about 0.5 millionths (0.0000005) of an inch,and more preferably at least about one millionth (0.000001) of an inch.The upper thickness range is not critical and is generally dependentupon considerations such as cost. Generally, however, the layercomprised of refractory metal or refractory metal alloy should not bethicker than about 50 millionths (0.00005) of an inch, preferably about15 millionths (0.000015) of an inch, and more preferably about 10millionths (0.000010) of an inch.

[0053] Generally the refractory metal or refractory metal alloy layerfunctions, inter alia, to improve the adhesion of a layer comprised ofrefractory metal compound, refractory metal alloy compound, reactionproducts of refractory metal or refractory metal alloy, oxygen andnitrogen to the electroplated article. Thus, the refractory metal orrefractory metal alloy layer generally has a thickness which is at leasteffective to improve the adhesion of a layer comprised of refractorymetal compound, refractory metal alloy compound, and reaction productsof a refractory metal or refractory metal alloy, oxygen and nitrogen tothe electroplated article.

[0054] In a preferred embodiment of the present invention the refractorymetal layer is comprised of zirconium, titanium, or zirconium-titaniumalloy, preferably zirconium or zirconium-titanium alloy, and isdeposited by physical vapor deposition processes such as, for example,ion sputtering or electron beam evaporation.

[0055] The layer comprised of refractory metal compound, refractorymetal alloy compound, or reaction products of refractory metal orrefractory metal alloy compound, oxygen and nitrogen generally has athickness which is at least about 2 millionths (0.000002) of an inch,preferably at least about 4 millionths (0.000004) of an inch, and morepreferably at least about 6 millionths (0.000006) of an inch. The upperthickness range is generally not critical and is dependent uponconsiderations such as cost. Generally a thickness of about 30millionths (0.00003) of an inch, preferably about 25 millionths(0.000025) of an inch, and more preferably about 20 millionths(0.000020) of an inch should not be exceeded.

[0056] This layer generally provides wear resistance, abrasionresistance and the desired color or appearance. This layer is preferablycomprised of zirconium nitride or zirconium-titanium alloy nitride whichhas the color of brass. The thickness of this layer is at leasteffective to provide wear resistance, abrasion resistance, and thedesired color or appearance.

[0057] In another embodiment of the invention a sandwich layer comprisedof alternating layers of a non-precious refractory metal compound ornon-precious refractory metal alloy compound and a non-preciousrefractory metal or non-precious refractory metal alloy is depositedover the refractory metal or refractory metal alloy layer such aszirconium or zirconium-titanium alloy. An exemplary structure of thisembodiment is illustrated in FIG. 4 wherein 22 represents the refractorymetal or refractory metal alloy layer, preferably zirconium orzirconium-titanium alloy, 26 represents the sandwich layer, 28represents a non-precious refractory metal compound layer ornon-precious refractory metal alloy compound layer, and 30 represents anon-precious refractory metal layer or non-precious refractory metalalloy layer.

[0058] The non-precious refractory metals and non-precious refractorymetal alloys comprising layers 30 include hafnium, tantalum, titanium,zirconium, zirconium-titanium alloy, zirconium-hafnium alloy, and thelike; preferably zirconium, titanium, or zirconium-titanium alloy; andmore preferably zirconium or zirconium-titanium alloy.

[0059] The non-precious refractory metal compounds and non-preciousrefractory metal alloy compounds comprising layers 28 include hafniumcompounds, tantalum compounds, titanium compounds, zirconium compounds,and zirconium-titanium alloy compounds; preferably titanium compounds,zirconium compounds, or zirconium-titanium alloy compounds; and morepreferably zirconium compounds or zirconium-titanium alloy compounds.These compounds are selected from nitride, carbides and carbonitrides,with the nitride being preferred. Thus, the titanium compound isselected from titanium nitrides, titanium carbide and titaniumcarbonitride, with titanium nitride being preferred. The zirconiumcompound is selected from zirconium nitride, zirconium carbide andzirconium carbonitride, with zirconium nitride being preferred.

[0060] The sandwich layer 26 generally has an average thickness of fromabout 50 millionths (0.00005) of an inch to about one millionth(0.000001) of an inch, preferably from about 40 millionths (0.00004) ofan inch to about two millionths (0.000002) of an inch, and morepreferably from about 30 millionths (0.00003) of an inch to about threemillionths (0.000003) of an inch.

[0061] Each of layers 28 and 30 generally has a thickness of at leastabout 0.002 millionths (0.00000002) of an inch, preferably at leastabout 0.1 millionths (0.0000001) of an inch, and more preferably atleast about 0.5 millionths (0.0000005) of an inch. Generally, layers 28and 30 should not be thicker than about 25 millionths (0.000025) of aninch, preferably about 10 millionths (0.00001) of an inch, and morepreferably about 5 millionths (0.000005) of an inch.

[0062] A method of forming the sandwich layer 26 is by utilizing ionsputter plating to deposit a layer 30 of non-precious refractory metalsuch as zirconium or titanium followed by reactive ion sputter platingto deposit a layer 28 of non-precious refractory metal nitride such aszirconium nitride or titanium nitride.

[0063] Preferably the flow rate of nitrogen gas is varied (pulsed)during the reactive ion sputter plating between zero (no nitrogen gas isintroduced) to the introduction of nitrogen at a desired value to formmultiple alternating layers of metal 30 and metal nitride 28 in thesandwich layer 26.

[0064] The number of alternating layers of refractory metal 30 andrefractory metal compound layers 28 in sandwich layer 26 is generally atleast about 2, preferably at least about 4, and more preferably at leastabout 6. Generally, the number of alternating layers of refractory metal30 and refractory metal compound 30 in sandwich layer 26 should notexceed about 50, preferably about 40, and more preferably about 30.

[0065] In one embodiment of the invention, as illustrated in FIG. 4,vapor deposited over the sandwich layer 26 is a layer 32 comprised of anon-precious refractory metal compound or non-precious refractory metalalloy compound, preferably a nitride, carbide or carbonitride, and morepreferably a nitride.

[0066] Layer 32 is comprised of a hafnium compound, a tantalum compound,a titanium compound, a zirconium-titanium alloy compound, or a zirconiumcompound, preferably a titanium compound, a zirconium-titanium alloycompound, or a zirconium compound, and more preferably a zirconiumcompound or a zirconium-titanium alloy compound. The titanium compoundis selected from titanium nitride, titanium carbide, and titaniumcarbonitride, with titanium nitride being preferred. The zirconiumcompound is selected from zirconium nitride, zirconium carbonitride, andzirconium carbide, with zirconium nitride being preferred.

[0067] Layer 32 provides wear and abrasion resistance and the desiredcolor or appearance, such as for example, polished brass. Layer 32 isdeposited on layer 26 by any of the well known and conventional physicalvapor deposition techniques such as reactive ion sputtering.

[0068] Layer 32 has a thickness at least effective to provide abrasionresistance and/or the color of brass. Generally, this thickness is atleast 2 millionths (0.000002) of an inch, preferably at least 4millionths (0.000004) of an inch, and more preferably at least 6millionths (0.000006) of an inch. The upper thickness range is generallynot critical and is dependent upon considerations such as cost.Generally a thickness of about 30 millionths (0.00003) of an inch,preferably about 25 millionths (0.000025) of an inch, and morepreferably about 20 millionths (0.000020) of an inch should not beexceeded.

[0069] Zirconium nitride is the preferred coating material as it mostclosely provides the appearance of polished brass.

[0070] In one embodiment of the invention, as illustrated in FIG. 4, alayer 34 comprised of the reaction products of a non-precious refractorymetal or metal alloy, an oxygen containing gas such as oxygen, andnitrogen is deposited onto layer 32. The metals that may be employed inthe practice of this invention are those which are capable of formingboth a metal oxide and a metal nitride under suitable conditions, forexample, using a reactive gas comprised of oxygen and nitrogen. Themetals may be, for example, tantalum, hafnium, zirconium,zirconium-titanium alloy, and titanium, preferably titanium,zirconium-titanium alloy and zirconium, and more preferably zirconiumand zirconium-titanium alloy.

[0071] The reaction products of the metal or metal alloy, oxygen andnitrogen are generally comprised of the metal or metal alloy oxide,metal or metal alloy nitride and metal or metal alloy oxy-nitride. Thus,for example, the reaction products of zirconium, oxygen and nitrogencomprise zirconium oxide, zirconium nitride and zirconium oxy-nitride.

[0072] The layer 34 can be deposited by a well known and conventionalphysical vapor deposition techniques, including reactive ion sputteringof a pure metal target and a gas or a composite target of oxides,nitride and/or metals.

[0073] These metal oxides and metal nitride including zirconium oxideand zirconium nitride alloys and their preparation and deposition areconventional and well known and are disclosed, inter alia, in U.S. Pat.No. 5,367,285, the disclosure of which is incorporated herein byreference.

[0074] The metal, oxygen and nitrogen reaction products containing layer34 generally has a thickness of at least about 0.1 millionths(0.0000001) of an inch, preferably at least about 0.15 millionths(0.00000015) of an inch, and more preferably at least about 0.2millionths (0.0000002) of an inch. Generally, the metal oxy-nitridelayer should not be thicker than about one millionth (0.000001) of aninch, preferably about 0.5 millionths (0.0000005) of an inch, and morepreferably about 0.4 millionths (0.0000004) of an inch.

[0075] In another embodiment, as illustrated in FIG. 5, instead of thelayer 34 comprised of the reaction products of a refractory metal orrefractory metal alloy, oxygen and nitrogen being deposited on layer 32a layer 36 comprised of non-precious refractory metal oxide orrefractory metal alloy oxide is applied by physical vapor depositiononto layer 32. The refractory metal oxides and refractory metal alloyoxides of which layer 36 is comprised include, but are not limited to,hafnium oxide, tantalum oxide, zirconium oxide, titanium oxide, andzirconium-titanium alloy oxide, preferably titanium oxide, zirconiumoxide, and zirconium-titanium alloy oxide, and more preferably zirconiumoxide and zirconium-titanium alloy oxide.

[0076] Layer 36 has a thickness of at least about 0.1 millionths(0.0000001) of an inch, preferably at least about 0.15 millionths(0.00000015) of an inch, and more preferably at least about 0.2millionths (0.0000002) of an inch. Generally the metal or metal alloyoxide layer 36 should not be thicker than about 2 millionths (0.000002)of an inch, preferably about 1.5 millionths (0.0000015) of an inch, andmore preferably about one millionth (0.000001) of an inch.

[0077]FIG. 6 illustrates an article substrate 12 having a bright nickellayer 16 electroplated on its surface and a chrome layer 20electroplated on the bright nickel layer 16. On the electroplated chromelayer are deposited by physical vapor deposition, after the substratearticle 12 having electroplated layers 16 and 20 thereon has beensubjected to pulse blow drying, layer 22 comprised of zirconium,sandwich layer 26 comprised of alternating layers 28 and 30 comprisedof, respectively, zirconium nitride and zirconium, layer 32 comprised ofzirconium nitride, and layer 34 comprised of the reaction products ofzirconium, oxygen and nitrogen.

[0078] In order that the invention may be more readily understood thefollowing example is provided. The example is illustrative and does notlimit the invention thereof.

EXAMPLE I

[0079] Brass faucets are placed in a conventional soak cleaner bathcontaining the standard and well known soaps, detergents, defloculantsand the like which is maintained at a pH of 8.9-9.2 and a temperature of180-200° F. for about 10 minutes. The brass faucets are then placed in aconventional ultrasonic alkaline cleaner bath. The ultrasonic cleanerbath has a pH of 8.9-9.2, is maintained at a temperature of about160-180° F., and contains the conventional and well known soaps,detergents, defloculants and the like. After the ultrasonic cleaning thefaucets are rinsed and placed in a conventional alkaline electro cleanerbath. The electro cleaner bath is maintained at a temperature of about140-180° F., a pH of about 10.5-11.5, and contains standard andconventional detergents. The faucets are then rinsed twice and placed ina conventional acid activator bath. The acid activator bath has a pH ofabout 2.0-3.0, is at an ambient temperature, and contains a sodiumfluoride based acid salt. The faucets are then rinsed twice and placedin a bright nickel plating bath for about 12 minutes. The bright nickelbath is generally a conventional bath which is maintained at atemperature of about 130-150° F., a pH of about 4.0, contains NiSO₄,NiCL₂, boric acid, and brighteners. A bright nickel layer of an averagethickness of about 400 millionths (0.0004) of an inch is deposited onthe faucet surface. The bright nickel plated faucets are rinsed threetimes and then placed in a conventional, commercially availablehexavalent chromium plating bath using conventional chromium platingequipment for about seven minutes. The hexavalent chromium bath is aconventional and well known bath which contains about 32 ounces/gallonof chromic acid. The bath also contains the conventional and well knownchromium plating additives. The bath is maintained at a temperature ofabout 112-116° F., and utilizes a mixed sulfate/fluoride catalyst. Thechromic acid to sulfate ratio is about 200:1. A chromium layer of about10 millionths (0.00001) of an inch is deposited on the surface of thebright nickel layer. The faucets are thoroughly rinsed in deionizedwater.

[0080] The electroplated faucets are placed on a rack and the rack movesthrough a pulse blow dryer manufactured by LPW-Anlagen GmbH of Germanyand described in European patent application EP 0486 711 A1. The blowdryer is equipped with a row of small nozzles which emit pulsating airjets at 80 psi. The dryer is maintained at a temperature of 130° F. Theelectroplated faucets remain in the pulse blow dryer a total of 210seconds, with the rack moving through the dryer two feet in fiveseconds. The rack remains motionless for 37 seconds and then advancesagain. The pulses last for about 20 miliseconds. The faucets are removedfrom the pulse blow dryer and are placed in a cathodic arc evaporationplating vessel. The vessel is generally a cylindrical enclosurecontaining a vacuum chamber which is adapted to be evacuated by means ofpumps. A source of argon gas is connected to the chamber by anadjustable valve for varying the rate of flow of argon into the chamber.In addition, a source of nitrogen gas is connected to the chamber by anadjustable valve for varying the rate of flow of nitrogen into thechamber.

[0081] A cylindrical cathode is mounted in the center of the chamber andconnected to negative outputs of a variable D.C. power supply. Thepositive side of the power supply is connected to the chamber wall. Thecathode material comprises zirconium.

[0082] The plated faucets are mounted on spindles, 16 of which aremounted on a ring around the outside of the cathode. The entire ringrotates around the cathode while each spindle also rotates around itsown axis, resulting in a so-called planetary motion which providesuniform exposure to the cathode for the multiple faucets mounted aroundeach spindle. The ring typically rotates at several rpm, while eachspindle makes several revolutions per ring revolution. The spindles areelectrically isolated from the chamber and provided with rotatablecontacts so that a bias voltage may be applied to the substrates duringcoating.

[0083] The vacuum chamber is evacuated to a pressure of about 5×10⁻³millibar and heated to about 150° C.

[0084] The electroplated faucets are then subjected to a high-bias arcplasma cleaning in which a (negative) bias voltage of about 500 volts isapplied to the electroplated faucets while an arc of approximately 500amperes is struck and sustained on the cathode. The duration of thecleaning is approximately five minutes.

[0085] Argon gas is introduced at a rate sufficient to maintain apressure of about 3×10⁻² millibars. A layer of zirconium having anaverage thickness of about four millionths (0.000004) of an inch isdeposited on the chrome plated faucets during a three minute period. Thecathodic arc deposition process comprises applying D.C. power to thecathode to achieve a current flow of about 500 amps, introducing argongas into the vessel to maintain the pressure in the vessel at about1×10⁻² millibar, and rotating the faucets in a planetary fashiondescribed above.

[0086] After the zirconium layer is deposited the sandwich layer isapplied onto the zirconium layer. A flow of nitrogen is introduced intothe vacuum chamber periodically while the arc discharge continues atapproximately 500 amperes. The nitrogen flow rate is pulsed, i.e.changed periodically from a maximum flow rate, sufficient to fully reactthe zirconium atoms arriving at the substrate to form zirconium nitride,and a minimum flow rate equal to zero or some lower value not sufficientto fully react with all the zirconium. The period of the nitrogen flowpulsing is one to two minutes (30 seconds to one minute on, then off).The total time for pulsed deposition is about 15 minutes, resulting in asandwich stack with 10 to 15 layers of thickness of about one to 1.5millionths of an inch each. The deposited material in the sandwich layeralternates between fully reacted zirconium nitride and zirconium metal(or substoichiometric ZrN with much smaller nitrogen content).

[0087] After the sandwich layer is deposited, the nitrogen flow rate isleft at its maximum value (sufficient to form fully reacted zirconiumnitride) for a time of five to ten minutes to form a thicker “colorlayer” on top of the sandwich layer. After this zirconium nitride layeris deposited, an additional flow of oxygen of approximately 0.1 standardliters per minute is introduced for a time of thirty seconds to oneminute, while maintaining nitrogen and argon flow rates at theirprevious values. A thin layer of mixed reaction products is formed(zirconium oxy-nitride), with thickness approximately 0.2 to 0.5millionths of an inch. The arc is extinguished at the end of this lastdeposition period, the vacuum chamber is vented and the coatedsubstrates removed.

What is claimed is:
 1. A process of depositing a multi layer coating onat least a portion of an article surface comprising: depositing byelectroplating at least one electroplated layer on at least a portion ofsaid article to form an electroplated article; subjecting said articlehaving said at least one electroplated layer to pulse blow drying to drysaid article and remove any liquid spots therefrom; and depositing byphysical vapor deposition at least one layer on at least a portion ofsaid electroplated layer.
 2. The process of claim 1 wherein saidelectroplating comprises electroplating at least one layer selected fromcopper, nickel and chrome on at least a portion of said article surface.3. The process of claim 2 wherein at least one layer selected fromrefractory metal, refractory metal alloy, refractory metal compound, andrefractory metal alloy compound is vapor deposited on at least a portionof said at least one electroplated layer.
 4. The process of claim 3wherein said refractory metal and refractory metal alloy is selectedfrom zirconium, titanium and zirconium-titanium alloy.
 5. The process ofclaim 4 wherein said refractory metal and refractory metal alloy isselected from zirconium and zirconium-titanium alloy.
 6. The process ofclaim 3 wherein said refractory metal compound and refractory metalalloy compound is selected from nitrides, carbides, carbonitrides,oxides and reaction products of refractory metal or refractory metalalloy, oxygen and nitrogen.
 7. The process of claim 6 wherein saidrefractory metal compound and refractory metal alloy compound isselected from nitrides, oxides and reaction products of refractory metalor refractory metal alloy, oxygen and nitrogen.
 8. The process of claim7 wherein said refractory metal compound and refractory metal alloycompound is selected from zirconium nitride, zirconium oxide, reactionproducts of zirconium, oxygen and nitrogen, titanium nitride, titaniumoxide, reaction products of titanium, oxygen and nitrogen,zirconium-titanium alloy nitride, zirconium-titanium alloy oxide, andreaction products of zirconium-titanium alloy, oxygen and nitrogen. 9.The process of claim 8 wherein said refractory metal compound andrefractory metal alloy compound is selected from zirconium oxide,zirconium nitride, reaction products of zirconium, oxygen and nitrogen,zirconium-titanium alloy nitride, zirconium-titanium alloy oxide, andreaction products of zirconium-titanium alloy, oxygen and nitrogen. 10.The process of claim 7 wherein said electroplating compriseselectroplating at least one layer comprised of copper on at least aportion of the surface of said article to provide at least oneelectroplated copper layer, electroplating at least layer comprised ofnickel on said at least one electroplated copper layer to provide atleast one electroplated nickel layer, and electroplating at least onelayer comprised of chrome in said at least one electroplated nickellayer to provide at least one electroplated chrome layer.
 11. Theprocess of claim 10 wherein at least one layer selected from refractorymetal and refractory metal alloy is vapor deposited on at least aportion of said electroplated chrome layer.
 12. The process of claim 11wherein said refractory metal and refractory metal alloy is selectedfrom zirconium, titanium and zirconium-titanium alloy.
 13. The processof claim 12 wherein said refractory metal and refractory metal alloy isselected from zirconium and zirconium-titanium alloy.
 14. The process ofclaim 13 wherein a sandwich coating comprised of alternating layers ofzirconium or zirconium-titanium alloy and zirconium nitride orzirconium-titanium alloy nitride is vapor deposited over said zirconiumor zirconium-titanium alloy layer.
 15. The process of claim 14 wherein azirconium nitride or zirconium-titanium alloy nitride layer is vapordeposited over said sandwich layer.
 16. The process of claim 15 whereina zirconium oxide or zirconium-titanium oxide layer is vapor depositedover said zirconium nitride or zirconium-titanium alloy nitride layer.17. The process of claim 15 wherein a layer comprised of the reactionproducts of zirconium or zirconium-titanium alloy, oxygen and nitrogenis vapor deposited over said zirconium nitride or zirconium-titaniumalloy nitride layer.
 18. The process of claim 13 wherein a layercomprised of zirconium nitride or zirconium-titanium alloy nitride isvapor deposited over said zirconium or zirconium-titanium alloy layer.19. The process of claim 18 wherein a layer comprised of zirconium oxideor zirconium-titanium alloy oxide is vapor deposited over said zirconiumnitride or zirconium-titanium nitride alloy layer.
 20. The process ofclaim 18 wherein a layer comprised of the reaction products of zirconiumor zirconium-titanium alloy layer, oxygen and nitrogen is vapordeposited over said zirconium nitride or zirconium-titanium alloynitride layer.
 21. The process of claim 1 wherein said electroplatingcomprises electroplating at least one layer selected from nickel andchrome on at least a portion of said article surface.
 22. The process ofclaim 21 wherein at least one layer selected from refractory metal,refractory metal alloy, refractory metal compound, and refractory metalalloy compound is vapor deposited on at least a portion of said at leastone electroplated layer.
 23. The process of claim 22 wherein saidrefractory metal and refractory metal alloy is selected from zirconium,titanium and zirconium-titanium alloy.
 24. The process of claim 23wherein said refractory metal and refractory metal alloy is selectedfrom zirconium and zirconium-titanium alloy.
 25. The process of claim 22wherein said refractory metal compound and refractory metal alloycompound is selected from nitrides, carbides, carbonitrides, oxides andreaction products of refractory metal or refractory metal alloy, oxygenand nitrogen.
 26. The process of claim 25 wherein said refractory metalcompound and refractory metal alloy compound is selected from nitrides,oxides and reaction products of refractory metal or refractory metalalloy, oxygen and nitrogen.
 27. The process of claim 26 wherein saidrefractory metal compound and refractory metal alloy compound isselected from zirconium nitride, zirconium oxide, reaction products ofzirconium, oxygen and nitrogen, titanium nitride, titanium oxide,reaction products of titanium, oxygen and nitrogen, zirconium-titaniumalloy nitride, zirconium-titanium alloy oxide, and reaction products ofzirconium-titanium alloy, oxygen and nitrogen.
 28. The process of claim27 wherein said refractory metal compound and refractory metal alloycompound is selected from zirconium oxide, zirconium nitride, reactionproducts of zirconium, oxygen and nitrogen, zirconium-titanium alloynitride, zirconium-titanium alloy oxide, and reaction products ofzirconium-titanium alloy, oxygen and nitrogen.
 29. The process of claim26 wherein said electroplating comprises electroplating at least onelayer comprised of nickel on at least a portion of the surface of saidarticle to provide at least one electroplated nickel layer, andelectroplating at least one layer comprised of chrome on said at leastone electroplated nickel layer to provide at least one electroplatedchrome layer.
 30. The process of claim 29 wherein at least one layerselected from refractory metal and refractory metal alloy is vapordeposited on at least a portion of said electroplated chrome layer. 31.The process of claim 30 wherein said refractory metal and refractorymetal alloy is selected from zirconium, titanium and zirconium-titaniumalloy.
 32. The process of claim 31 wherein said refractory metal andrefractory metal alloy is selected from zirconium and zirconium-titaniumalloy.
 33. The process of claim 32 wherein a sandwich coating comprisedof alternating layers of zirconium or zirconium-titanium alloy andzirconium nitride or zirconium-titanium alloy nitride is vapor depositedover said zirconium or zirconium-titanium alloy layer.
 34. The processof claim 33 wherein a zirconium nitride or zirconium-titanium alloynitride layer is vapor deposited over said sandwich layer.
 35. Theprocess of claim 34 wherein a zirconium oxide or zirconium-titaniumoxide layer is vapor deposited over said zirconium nitride orzirconium-titanium alloy nitride layer.
 36. The process of claim 34wherein a layer comprised of the reaction products of zirconium orzirconium-titanium alloy, oxygen and nitrogen is vapor deposited oversaid zirconium nitride or zirconium-titanium alloy nitride layer. 37.The process of claim 32 wherein a layer comprised of zirconium nitrideor zirconium-titanium alloy nitride is vapor deposited over saidzirconium or zirconium-titanium alloy layer.
 38. The process of claim 37wherein a layer comprised of zirconium oxide or zirconium-titanium alloyoxide is vapor deposited over said zirconium nitride orzirconium-titanium nitride alloy layer.
 39. The process of claim 37wherein a layer comprised of the reaction products of zirconium orzirconium-titanium alloy layer, oxygen and nitrogen is vapor depositedover said zirconium nitride or zirconium-titanium alloy nitride layer.38. The process of claim 1 wherein at least one layer selected fromrefractory metal, refractory metal alloy, refractory metal compound, andrefractory metal alloy compound is vapor deposited on at least a portionof said at least one electroplated layer.
 39. The process of claim 38wherein said refractory metal and refractory metal alloy is selectedfrom zirconium, titanium and zirconium-titanium alloy.
 40. The processof claim 39 wherein said refractory metal and refractory metal alloy isselected from zirconium and zirconium-titanium alloy.
 41. The process ofclaim 38 wherein said refractory metal compound and refractory metalalloy compound is selected from nitrides, carbides, carbonitrides,oxides and reaction products of refractory metal or refractory metalalloy, oxygen and nitrogen.
 42. The process of claim 41 wherein saidrefractory metal compound and refractory metal alloy compound isselected from nitride, oxides and reaction products of refractory metalor refractory metal alloy, oxygen and nitrogen.
 43. The process of claim42 wherein said refractory metal compound and refractory metal alloycompound is selected from zirconium nitride, zirconium oxide, reactionproducts of zirconium, oxygen and nitrogen, titanium nitride, titaniumoxide, reaction products of titanium, oxygen and nitrogen,zirconium-titanium alloy nitride, zirconium-titanium alloy oxide, andreaction products of zirconium-titanium alloy, oxygen and nitrogen. 44.The process of claim 43 wherein said refractory metal compound andrefractory metal alloy compound is selected from zirconium oxide,zirconium nitride, reaction products of zirconium, oxygen and nitrogen,zirconium-titanium alloy nitride, zirconium-titanium alloy oxide, andreaction products of zirconium-titanium alloy, oxygen and nitrogen. 45.The process of claim 1 wherein at least one layer selected fromrefractory metal and refractory metal alloy is vapor deposited on atleast a portion of said electroplated article.
 46. The process of claim45 wherein said refractory metal and refractory metal alloy is selectedfrom zirconium, titanium and zirconium-titanium alloy.
 47. The processof claim 46 wherein said refractory metal and refractory metal alloy isselected from zirconium and zirconium-titanium alloy.
 48. The process ofclaim 47 wherein a sandwich coating comprised of alternating layers ofzirconium or zirconium-titanium alloy and zirconium nitride orzirconium-titanium alloy nitride is vapor deposited over said zirconiumor zirconium-titanium alloy layer.
 49. The process of claim 48 wherein azirconium nitride or zirconium-titanium alloy nitride layer is vapordeposited over said sandwich layer.
 50. The process of claim 49 whereina zirconium oxide or zirconium-titanium oxide layer is vapor depositedover said zirconium nitride or zirconium-titanium alloy nitride layer.51. The process of claim 49 wherein a layer comprised of theoverreaction products of zirconium or zirconium-titanium alloy, oxygenand nitrogen is vapor deposited over said zirconium nitride orzirconium-titanium alloy nitride layer.
 52. The process of claim 47wherein a layer comprised of zirconium nitride or zirconium-titaniumalloy nitride is vapor deposited over said zirconium orzirconium-titanium alloy layer.
 53. The process of claim 52 wherein alayer comprised of zirconium oxide or zirconium-titanium alloy oxide isvapor deposited over said zirconium nitride or zirconium-titaniumnitride alloy layer.
 54. The process of claim 52 wherein a layercomprised of the reaction products of zirconium or zirconium-titaniumalloy layer, oxygen and nitrogen is vapor deposited over said zirconiumnitride or zirconium-titanium alloy nitride layer.
 55. The process ofclaim 1 wherein said article is comprised of metal or a metal alloy. 56.The process of claim 55 wherein said article is comprised of brass. 57.The process of claim 55 wherein said article is comprised of zinc. 58.The process of claim 1 wherein said article is comprised of plastic. 59.The process of claim 1 wherein said article is a faucet.
 60. The processof claim 1 wherein said article is door lock hardware.
 61. The processof claim 1 wherein said article is a lamp.